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Title: Vibrationally resolved photoelectron spectra of CuCN- and AgCN- and ab initio studies of the structure and bonding in CuCN

Abstract

Vibrationally resolved photoelectron spectroscopy is combined with ab initio calculations to investigate the structure and chemical bonding in CuCN, CuCN{sup -}, AgCN, and AgCN{sup -}. The photoelectron spectra were measured at two photon energies, 532 and 355 nm and only detachment to the ground state of the neutral was observed at both detachment energies. The adiabatic electron affinity and metal-C vibrational frequency were obtained to be 1.466 (0.010) eV and 480(30) cm-1, 1.588 (0.010) eV and 390(30) cm-1 for CuCN and AgCN, respectively. In the ab initio calculations, both CuCN and CuCN{sup -} were found to have linear C{sub {infinity}}{sub V} structures. Isocyanide CuNC and CuNC{sup -} were found to be 10.7 and 6.5 kcal/mol [at the CCSD(T)/6-311+G(3d)//CCSD(T)/6-311+G{sup *} level of theory] higher in energy. Cyclic structures were found to be transition states for the cyanide-isocyanide isomerization. The calculated electron binding energies and vibrational frequency are in good agreement with the experimental measurements. The combined experimental and theoretical efforts allow us to elucidate the structures of CuCN and CuCN{sup -}, and the nature of their chemical bonding. (c) 2000 American Institute of Physics.

Authors:
 [1];  [2];  [3];  [2]
  1. Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300 (United States)
  2. Department of Physics, Washington State University, Richland, Washington 99352 (United States)
  3. (United States)
Publication Date:
OSTI Identifier:
20215432
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 112; Journal Issue: 8; Other Information: PBD: 22 Feb 2000; Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; PHOTOELECTRON SPECTROSCOPY; VIBRATIONAL STATES; COPPER COMPOUNDS; SILVER COMPOUNDS; CYANIDES; CHEMICAL BONDS; MOLECULAR STRUCTURE; ANIONS; AFFINITY; ISOMERIZATION; BINDING ENERGY; EXPERIMENTAL DATA; THEORETICAL DATA

Citation Formats

Boldyrev, Alexander I., Li, Xi, W. R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, MS K8-88, P.O. Box 999, Richland, Washington 99352, and Wang, Lai-Sheng. Vibrationally resolved photoelectron spectra of CuCN- and AgCN- and ab initio studies of the structure and bonding in CuCN. United States: N. p., 2000. Web. doi:10.1063/1.480516.
Boldyrev, Alexander I., Li, Xi, W. R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, MS K8-88, P.O. Box 999, Richland, Washington 99352, & Wang, Lai-Sheng. Vibrationally resolved photoelectron spectra of CuCN- and AgCN- and ab initio studies of the structure and bonding in CuCN. United States. doi:10.1063/1.480516.
Boldyrev, Alexander I., Li, Xi, W. R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, MS K8-88, P.O. Box 999, Richland, Washington 99352, and Wang, Lai-Sheng. Tue . "Vibrationally resolved photoelectron spectra of CuCN- and AgCN- and ab initio studies of the structure and bonding in CuCN". United States. doi:10.1063/1.480516.
@article{osti_20215432,
title = {Vibrationally resolved photoelectron spectra of CuCN- and AgCN- and ab initio studies of the structure and bonding in CuCN},
author = {Boldyrev, Alexander I. and Li, Xi and W. R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, MS K8-88, P.O. Box 999, Richland, Washington 99352 and Wang, Lai-Sheng},
abstractNote = {Vibrationally resolved photoelectron spectroscopy is combined with ab initio calculations to investigate the structure and chemical bonding in CuCN, CuCN{sup -}, AgCN, and AgCN{sup -}. The photoelectron spectra were measured at two photon energies, 532 and 355 nm and only detachment to the ground state of the neutral was observed at both detachment energies. The adiabatic electron affinity and metal-C vibrational frequency were obtained to be 1.466 (0.010) eV and 480(30) cm-1, 1.588 (0.010) eV and 390(30) cm-1 for CuCN and AgCN, respectively. In the ab initio calculations, both CuCN and CuCN{sup -} were found to have linear C{sub {infinity}}{sub V} structures. Isocyanide CuNC and CuNC{sup -} were found to be 10.7 and 6.5 kcal/mol [at the CCSD(T)/6-311+G(3d)//CCSD(T)/6-311+G{sup *} level of theory] higher in energy. Cyclic structures were found to be transition states for the cyanide-isocyanide isomerization. The calculated electron binding energies and vibrational frequency are in good agreement with the experimental measurements. The combined experimental and theoretical efforts allow us to elucidate the structures of CuCN and CuCN{sup -}, and the nature of their chemical bonding. (c) 2000 American Institute of Physics.},
doi = {10.1063/1.480516},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 8,
volume = 112,
place = {United States},
year = {2000},
month = {2}
}